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CN101440264B - Aqueous adhesive composition and use thereof - Google Patents

Aqueous adhesive composition and use thereof Download PDF

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Publication number
CN101440264B
CN101440264B CN2008101818252A CN200810181825A CN101440264B CN 101440264 B CN101440264 B CN 101440264B CN 2008101818252 A CN2008101818252 A CN 2008101818252A CN 200810181825 A CN200810181825 A CN 200810181825A CN 101440264 B CN101440264 B CN 101440264B
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monomer
raw material
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material monomer
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CN101440264A (en
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高桥亚纪子
池谷真实
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention provides an aqueous adhesive composition suitable for an adhesive sheet that exhibits high levels of adhesiveness, high-temperature cohesive strength and edge peel resistance in a good balance and for preparation of the same. The composition is composed primarily of an acrylic polymer obtained by polymerizing a starting monomer material containing an alkyl(meth)acrylate as amain monomer and a silanol-forming monomer. The weight-average molecular weight of the polymer is 65x10<4> to 100x10<4>. The monomer material without the silanol-forming monomer is polymerized to produce a polymer having ethyl acetate of 7 to 17 mass %. The composition gives a post-crosslink adhesive having ethyl acetate of 20 to 55 mass %.

Description

Aqueous adhesive composition and utilization thereof
Technical field
The present invention relates to aqueous binder (being also referred to as pressure-sensitive adhesive (pressure-sensitive adhesive), down together) composition based on acrylic polymers and the adhesive sheet that uses said composition.
Advocate right of priority Japanese patent application 2007-302753 number that the present invention is based on application on November 22nd, 2007, the full content of this application is listed in this specification sheets as reference.
Background technology
Acrylic polymers is scattered in aqueous dispersion type (water-based) binder composition of the mode in the water, makes water as dispersion medium, therefore compares with solvent type binder composition, and is preferred on environmental health.In addition, this acrylic acid or the like aqueous adhesive composition has following advantage: form more excellent binder layer such as solvent resistance easily and have the adhesive sheet of this binder layer.
In this case, thirst for obtaining to form the acrylic acid or the like aqueous adhesive composition of more high performance adhesive sheet.If it is can provide the formation can be, then very useful balancedly bringing into play tackiness (binding property) for example, coherency (the particularly coherency under the hot environment (high temperature coherency)) and the terminal acrylic acid or the like aqueous adhesive composition of peeling off the adhesive sheet of multifrequency natures such as preventing property on the higher degree.
Summary of the invention
As one of method of the performance of attempting to improve the acrylic acid or the like aqueous adhesive composition, study about the structure (molecular-weight average etc.) of the polymkeric substance that constitutes said composition.For example in Japanese Patent Application Publication 2004-189933 communique, put down in writing the binder composition that in the aqueous dispersion type multipolymer of weight-average molecular weight more than 1,000,000, is combined with the aqueous dispersion type linking agent of Han oxazolinyl.Put down in writing in Japanese Patent Application Publication H02-150482 communique that to contain weight-average molecular weight be that weight-average molecular weight that 200,000～800,000 aqueous dispersion type multipolymer (I) and the monomer component that will contain the addition polymerization oxazoline are polymerized is the binder composition of 200,000～800,000 polymkeric substance (II).As other prior art document, can also enumerate: Japanese Patent Application Publication 2003-073637 communique, H08-165464 communique and 2001-131511 communique.
But above-mentioned existing technology all can not provide gratifying and realize the well balanced adhesive sheet of above-mentioned 3 characteristics and be applicable to the aqueous adhesive composition that forms this adhesive sheet with higher level.
One object of the present invention is to provide a kind of adhesive sheet, its tackiness (binding property) and coherency (the particularly coherency under the hot environment) height, and end peels off preventing property excellence, and it can balancedly realize this 3 characteristics with higher level.Another object of the present invention is to provide the aqueous adhesive composition that is applicable to the binder layer that has on the described adhesive sheet of formation.Other relevant purposes are to provide the method that is applicable to the aqueous adhesive composition that forms above-mentioned binder layer of making.
According to the present invention, provide based on acrylic polymers and this acrylic polymers to be scattered in (aqueous dispersion type) aqueous adhesive composition in the water.As the aforesaid propylene acids polymkeric substance of the main body (main component) of said composition, be to be principal monomer with (methyl) alkyl acrylate and to contain the silanol base and form the monomeric raw material monomer of property and carry out the acrylic polymers that polymerization (being typically letex polymerization) forms.The weight-average molecular weight (Mw) of the solvable composition of the tetrahydrofuran (THF) of this acrylic polymers (THF) is about 65 * 10 4～100 * 10 4In addition, above-mentioned raw material monomer is when removing composition after above-mentioned silanol base forms the property monomer from this raw material monomer and carry out polymerization, and the mass ratio (Ga) that forms the insoluble composition of ethyl acetate is about the raw material monomer of 7～17% polymkeric substance.Being constructed as follows of above-mentioned composition: the insoluble composition of ethyl acetate form by said composition crosslinked after tackiness agent in shared mass ratio (Gb) be about 20%～55%.
At this, as the polymkeric substance of the special object of the mass ratio (Ga) of the insoluble composition of above-mentioned ethyl acetate, be to remove the silanol base with above-mentioned raw material monomer to form the polymkeric substance (following also be referred to as sometimes " indicator polymerization thing ") that obtains when composition behind the property monomer carries out polymerization.The polymerization of this indicator polymerization thing, remove the raw material monomer (indicator polymerization thing raw material monomer) that above-mentioned silanol base forms the composition behind the property monomer replace the above-mentioned raw material monomer (acrylic polymers raw material monomer) from this raw material monomer except using, being aggregated under the identical condition during with the acrylic polymers that obtained by above-mentioned raw material monomer as the main component of above-mentioned binder composition carried out.At this, " identical condition " is meant that other polymerizing conditions (for example kind of the kind of polymerization temperature, polymerization time, initiator and consumption, chain-transfer agent and consumption etc.) except having or not silanol base formation property monomer are identical.
Above-mentioned binder composition, when carrying out polymerization with the above-mentioned composition of removing after the silanol base forms the property monomer, be to form the acrylic polymers that the raw material monomer of the indicator polymerization thing of Ga in above-mentioned scope is polymerized, it is to have the acrylic polymers of above-mentioned Mw.In this raw material monomer, contain above-mentioned silanol base in the insoluble composition of ethyl acetate shared mass ratio (Gb) mode in above-mentioned scope in above-mentioned tackiness agent after crosslinked and form the property monomer.If adopt described binder composition, then can form with coherency (high temperature coherency) under high-level equilibrium ground performance tackiness (stripping strength etc.), the hot environment and the terminal high performance adhesive (being typically binder layer) of peeling off these 3 characteristics of preventing property.
Above-mentioned silanol base forms the property monomer, can be to have the polymerizable compound that at least 1 (preferred more than 2, for example 2 or 3) can form the functional group (the silanol base forms property functional group) of silanol base (Si-OH) at 1 intramolecularly.As the preferred example of above-mentioned silanol base formation property functional group, can enumerate the functional group's (alkoxysilyl etc.) that forms the silanol base by hydrolysis.For example be preferably that to have 1 or 2 above carbonatomss at 1 intramolecularly be that the silanol base of 1～4 alkoxysilyl forms property monomer (monomer that contains alkoxysilyl).
In a preferred mode, above-mentioned silanol base formation property monomer is dialkoxy silicane (for example alkyl-dialkoxysilanes) or the trialkoxy silane with (methyl) acryl.Described organoalkoxysilane had 2 or 3 alkoxyl groups can be to be independently selected from methoxyl group and the oxyethyl group any respectively.It is preferably good and crosslinking reaction is good with the copolymerization of (methyl) alkyl acrylate that described silanol base forms the property monomer.The copolymerization ratio of silanol base formation property monomer in aforesaid propylene acids polymkeric substance can be for example about 0.005～about 0.035 quality %.
Described acrylic polymers forms the monomeric raw material monomer of property and carries out letex polymerization and obtain for the chain-transfer agent of about 0.025～about 0.035 mass parts will contain above-mentioned silanol base by using with respect to these raw material monomer 100 mass parts.If carry out letex polymerization in this way, then obtain the acrylic polymers of Mw in above-mentioned preferable range easily.In addition, when removing above-mentioned silanol base with above-mentioned raw material monomer and form the monomeric composition of property and carry out polymerization, obtain the indicator polymerization thing of Ga in above-mentioned preferable range easily.The composition that contains the acrylic polymers that obtains thus can form the tackiness agent of balancedly realizing above-mentioned 3 characteristics with higher level.
In one of optimal way of binder composition disclosed herein, above-mentioned raw material monomer contains methacrylic acid.Above-mentioned raw material monomer more preferably contains vinylformic acid and methacrylic acid simultaneously.The binder composition that uses the raw material monomer of described composition and obtain, can form the tackiness agent of the good and following excellent performance of not only above-mentioned 3 characteristics, described performance is: make rubber-like foam (being typically sheet) such as urethane foam carry out recoverable deformation along the surface shape (can be curved surface, uneven surface etc.) that is attached body, resist the screen resilience that this foam returns to original form, make shape (that is performance of the screen resilience of anti-foams, after this foam remains above-mentioned recoverable deformation.Below be also referred to as " the anti-rebound resilience of foams " sometimes).That is, can form the tackiness agent of peeling off preventing property and these 4 characteristics of the anti-rebound resilience of foams with high-level equilibrium ground realization tackiness, high temperature coherency, end.
State in the use in the mode of raw material monomer of the composition that contains vinylformic acid and methacrylic acid, vinylformic acid that contains in the above-mentioned raw material monomer and the mass ratio of methacrylic acid (AA:MAA) for example can be set in the scope of about 1:10～about 10:1.The binder composition that uses the raw material monomer of described composition to obtain can form the tackiness agent (particularly showing more good high-temperature coherency and the anti-elastic tackiness agent of foams) of balancedly realizing above-mentioned 4 characteristics with higher level.
Any binder composition disclosed herein can further contain tackifier.The cooperation ratio of these tackifier for example can be set at the scope of about 5～about 40 mass parts (is benchmark with the solids component) with respect to aforesaid propylene acids polymkeric substance 100 mass parts.The binder composition of described composition can form with higher level and balancedly realize the tackiness agent of above-mentioned 3 characteristics and have the high performance adhesive sheet of this tackiness agent (being typically binder layer).
According to the present invention, provide adhesive sheet with the binder layer that uses any one binder composition disclosed herein and form.The adhesive sheet of described formation can be with coherency under high-level equilibrium ground realization tackiness (stripping strength etc.), the hot environment and the terminal high performance adhesive sheet of peeling off these 3 characteristics of preventing property.
Description of drawings
Fig. 1 is a sectional view of schematically representing a configuration example of adhesive sheet of the present invention.
Fig. 2 is a sectional view of schematically representing another configuration example of adhesive sheet of the present invention.
Fig. 3 is a sectional view of schematically representing another configuration example of adhesive sheet of the present invention.
Fig. 4 is a sectional view of schematically representing another configuration example of adhesive sheet of the present invention.
Fig. 5 is a sectional view of schematically representing another configuration example of adhesive sheet of the present invention.
Fig. 6 is a sectional view of schematically representing another configuration example of adhesive sheet of the present invention.
Embodiment
Below, preferred implementation of the present invention is described.In addition, beyond the item of mentioning especially in this specification sheets to implementing item essential to the invention, can be used as based on the item of those skilled in the art's design of the state of the art and understand.The present invention can implement based on the technology general knowledge of disclosed content and this area in this specification sheets.
Acrylic polymers in the technology disclosed herein is the polymkeric substance that is formed by the raw material monomer polymerization (being typically letex polymerization) of stipulating.Above-mentioned raw material monomer with (methyl) alkyl acrylate, be that (methyl) acrylate of alkyl alcohol is principal monomer (a main composition monomer).Comprise vinylformic acid and methacrylic acid at this so-called " (methyl) vinylformic acid ".In addition, so-called " is principal monomer with (methyl) alkyl acrylate " is meant that the ratio of (methyl) alkyl acrylate shared content (is their total content) in the total amount of above-mentioned raw material monomer surpasses 50 quality % when (methyl) alkyl acrylate of containing more than 2 kinds.This (methyl) alkyl acrylate contains proportional, for example can be in the 50 quality % and the scope below the 99.8 quality % that surpass above-mentioned raw material monomer.Preferably (methyl) alkyl acrylate contains proportional raw material monomer for about 80 quality % above (being typically about 80～about 99.8 quality %), the raw material monomer of more preferably about 85 quality % above (being typically about 85～about 99.5 quality %).(methyl) alkyl acrylate shared ratio in raw material monomer can be (to be typically about 90～about 99 quality %) more than about 90 quality %.(being total to) polymerization ratio of (methyl) alkyl acrylate in this ratio and the acrylic polymers that this raw material monomer polymerization is obtained is roughly corresponding.
(methyl) alkyl acrylate that constitutes above-mentioned raw material monomer can be to be selected from following formula (1) CH 2=C (R 1) COOR 2(1)
The expression compound in more than a kind or 2 kinds.At this, the R in the following formula (1) 1Be hydrogen atom or methyl.In addition, the R in this formula (1) 2Be that carbonatoms is 1～20 alkyl.As above-mentioned R 2Object lesson, can enumerate: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl, hexyl, heptyl, 2-ethylhexyl, iso-octyl, different nonyl, isodecyl etc.Wherein, preferred carbonatoms be 2～14 (below, sometimes such carbon atom number range is expressed as " C 2-14") alkyl, more preferably C 2-10Alkyl (for example butyl, 2-ethylhexyl etc.).
In a preferred mode, about 70 quality % above (more preferably from about more than the 90 quality %) are the R in the above-mentioned formula (1) in the total amount of (methyl) alkyl acrylate that contains in the above-mentioned raw material monomer 2Be C 2-10(more preferably C 4-8) (methyl) acrylate of alkyl alcohol.(methyl) alkyl acrylate that contains in this raw material monomer can all be in fact (methyl) vinylformic acid C 2-10Alkyl (more preferably C 4-8Alkyl) ester.For example, as (methyl) alkyl acrylate, can be contain separately the composition of butyl acrylate, separately contain 2-EHA composition, contain the raw material monomer of the composition etc. of 2 kinds of butyl acrylate and 2-EHAs.Contain in butyl acrylate and/or the raw material monomer of 2-EHA above-mentioned as the composition of (methyl) alkyl acrylate, the containing of butyl acrylate (BA) and 2-EHA (2EHA) proportional (mass ratio), for example can be about BA/2EHA=0/100～100/0 (preferred 0/100～70/30, more preferably 5/95～60/40).
Above-mentioned raw material monomer also contains silanol base formation property monomer except (methyl) alkyl acrylate as principal monomer.In other words, there is the silanol base to form the property monomer as copolymerization in the acrylic polymers of the main body of binder composition disclosed herein.It can be to have at least 1 monomer that can introduce in the tackiness agent that is formed by above-mentioned binder composition by the functional group of the crosslinking structure of condensation reaction (silanol condensation) generation of silanol base that this silanol base forms property monomer.As the monomeric preferred example of above-mentioned silanol base formation property, can enumerate: the silanol base formation property monomer (monomer that contains alkoxysilyl) that has at least 1 (preferred more than 2, for example 2 or 3) alkoxysilyl at 1 intramolecularly.From with the viewpoint of the copolymerization of (methyl) alkyl acrylate; the silanol base that preferably has ethene unsaturated groups such as acryl more than 1 or 2, methacryloyl (following sometimes acryl and methacryloyl are expressed as together " (methyl) acryl "), vinyl at 1 intramolecularly forms the property monomer; wherein, the silanol base formation property monomer that preferably has (methyl) acryl and alkoxysilyl (for example 1 (methyl) acryl and 2 or 3 alkoxysilyls) at 1 intramolecularly.
As the monomeric object lesson of described silanol base formation property, can enumerate: 3-methacryloxypropyl trimethoxy silane, 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl triethoxyl silane, 3-acryloxy propyl-triethoxysilicane, 3-methacryloxypropyl methyl dimethoxysilane, 3-acryloxy propyl group methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-acryloxy propyl group methyldiethoxysilane etc.In addition, as formation property of the silanol base beyond above-mentioned monomer, all right illustration: vinyltrimethoxy silane, vinyltriethoxysilane, 4-vinyl butyl Trimethoxy silane, 4-vinyl butyl triethoxyl silane, 8-vinyl octyl group Trimethoxy silane, 8-vinyl octyltri-ethoxysilane, 10-methacryloxy decyl Trimethoxy silane, 10-acryloxy decyl Trimethoxy silane, 10-methacryloxy decyl triethoxyl silane, 10-acryloxy decyl triethoxyl silane etc.Above-mentioned silanol base formation property monomer may be used alone, two or more kinds can also be used in combination.
Silanol base in the aforesaid propylene acids polymkeric substance forms the monomeric copolymerization ratio of property, and the weight-average molecular weight (Mw) that can be set at the solvable composition of THF of the mass ratio (Ga) of the insoluble composition of ethyl acetate that makes the These parameters polymkeric substance and aforesaid propylene acids polymkeric substance reaches respectively in the preferred value scope disclosed herein.In addition, the mass ratio (Gb) that also can be set at the insoluble composition of ethyl acetate that makes the tackiness agent after crosslinked reaches in the preferred value scope disclosed herein.For example, be about 0.005～about 0.035 quality % (more preferably about 0.01～about 0.03 quality %) by making silanol base formation property monomer shared ratio in above-mentioned raw material monomer total amount, can realize above-mentioned Ga, Mw and Gb aptly.
Above-mentioned raw material monomer can also contain other monomers (copolymer composition) as any composition except (methyl) alkyl acrylate and above-mentioned silanol base formation property monomer as principal monomer.Should " other monomers " can be selected from can with the various monomers of (methyl) alkyl acrylate copolymer as used herein in more than a kind or 2 kinds.For example, can be the various ethylene unsaturated monomers that 1 intramolecularly has ethene unsaturated groups such as (methyl) acryl, vinyl more than 1 or 2.
As the monomer that above-mentioned " other monomers " can adopt, for example can enumerate: ethylene unsaturated monomer (following be also referred to as sometimes " monomer that contains functional group ") with following various functional groups.
Ethene unsaturated monocarboxylic acids such as vinylformic acid, methacrylic acid, butenoic acid; Ethene unsaturated dicarboxylic acids such as toxilic acid, methylene-succinic acid, citraconic acid and acid anhydrides thereof etc. have the ethylene unsaturated monomer of carboxyl.
(methyl) vinylformic acid N-alkylaminoalkyls such as (methyl) vinylformic acid N-methylamino ethyl ester, (methyl) vinylformic acid N-ethylamino ethyl ester, (methyl) vinylformic acid N-tertiary butyl amino ethyl ester; (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, (methyl) vinylformic acid N such as N-diethylamino ethyl ester, N-dialkyl aminoalkyl ester etc. have amino ethylene unsaturated monomer.
(methyl) vinylformic acid hydroxyalkyl acrylates such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester; Vinyl alcohol, vinyl carbinol, N hydroxymethyl acrylamide etc. have the ethylene unsaturated monomer of hydroxyl.
Two acetone (methyl) acrylamide, two acetone (methyl) acrylate, acetoacetoxy groups methyl (methyl) acrylate, 2-(acetoacetoxy groups) ethyl (methyl) acrylate (being the acetylacetic ester of 2-hydroxyethyl (methyl) acrylate), 2-acetoacetoxy groups propyl group (methyl) acrylate, butyleneglycol-1,4-acrylate-acetylacetic ester (promptly 1, the vinylformic acid of 4-butyleneglycol/etheric acid diester), 1 intramolecularly have the compound of (methyl) acryl and ketone group (for example ethanoyl); Vinyl alkyl ketone such as ethenyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone (vinyl-C for example 1-7Alkyl ketone); Allyl group acetylacetic ester, vinyl acetylacetic ester, vinyl aceto-acetamide etc. have the ethylene unsaturated monomer of ketone group.
(methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide etc. have the ethylene unsaturated monomer of amide group.
(methyl) glycidyl acrylate, glycidyl allyl ether etc. have the ethylene unsaturated monomer of epoxy group(ing).
The above-mentioned monomer that contains functional group can only use a kind, also can be used in combination more than 2 kinds.As the monomer that contains functional group of preferred use, can enumerate ethylene unsaturated monomer (more preferably ethene unsaturated monocarboxylic acid) with carboxyl.Wherein, preferably use vinylformic acid and/or methacrylic acid.
In the raw material monomer that contains the described monomeric composition that contains functional group, can make the monomer that contains functional group (when containing more than 2 kinds for their total) (be typically about 0.5～about 12 mass parts) with respect to proportional for example being about below 12 mass parts of containing of (methyl) alkyl acrylate 100 mass parts.This ratio also can be to be about 8 mass parts following (being typically about 1～about 8 mass parts) with respect to (methyl) alkyl acrylate 100 mass parts.
The above-mentioned monomer that contains functional group can use with form the constituent of property monomer as raw material monomer as (methyl) alkyl acrylate of principal monomer and above-mentioned silanol base, helps to introduce cross-linking set to the acrylic polymers that is obtained by this raw material monomer.That is, described functional group (bridging property functional group) can become the cross-linking set that helps to be coupled to as required crosslinked (the being typically heat cross-linking) reaction between the functional group that linking agent had in this acrylic polymers and/or the functional group's (can be the bridging property functional group by the monomer copolymerization that contains functional group of the same race or not of the same race is introduced) that acrylic polymers had.Therefore, above-mentioned contain the monomeric kind of functional group and contain proportional (copolymerization ratio) can wait according to the crosslinking degree (cross-linking density) of the type of the kind of the linking agent that uses and consumption thereof, crosslinking reaction, expectation and set.For example, can set to make and remove the mass ratio (Ga) that above-mentioned silanol base forms the insoluble composition of ethyl acetate of the polymkeric substance (indicator polymerization thing) that obtains when composition behind the property monomer carries out polymerization with above-mentioned raw material monomer and can reach in the preferred value scope disclosed herein.In addition, the mass ratio (Gb) that can also set the insoluble composition of ethyl acetate that makes the tackiness agent after crosslinked can reach in the preferred numerical range disclosed herein.
As other examples of above-mentioned " other monomers ", can also enumerate: multifunctional (methyl) acrylate such as ethylene glycol bisthioglycolate (methyl) acrylate, dipropylene glycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, promptly 1 intramolecularly has the ethylene unsaturated monomer of (methyl) acryl more than 2.Above-mentioned multifunctional (methyl) acrylate can help to introduce branched structure or crosslinking structure to the acrylic polymers that is obtained by this raw material monomer with using as (methyl) alkyl acrylate of principal monomer constituent as raw material monomer.In the raw material monomer of the composition that contains multifunctional (methyl) acrylate, can make multifunctional (methyl) acrylate with respect to proportional for example being about below the 10 quality % of containing of (methyl) alkyl acrylate 100 mass parts.This ratio also can be below about 5 quality % of raw material monomer.Whether use multifunctional (methyl) acrylate and when using multifunctional (methyl) acrylate kind and contain proportionally, be preferably set to above-mentioned Ga and Mw can be reached in the preferred value scope disclosed herein.It also can be the raw material monomer that does not contain the composition of multifunctional (methyl) acrylate in fact.
Monomeric other examples that can use as above-mentioned " other monomers " can also be enumerated: vinyl acetate such as vinyl-acetic ester, propionate; Aromatic ethenyl compounds such as vinylbenzene, alpha-methyl styrene, Vinyl toluene; (methyl) acrylate of cyclic alcohol such as (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate; And ethylene unsaturated monomer such as (methyl) vinyl cyanide, N-(methyl) acryloyl morpholine, N-vinyl-2-Pyrrolidone etc.These monomeric usage ratios (being their overall proportion when containing more than 2 kinds) for example can be about below the 10 quality % with respect to (methyl) alkyl acrylate 100 mass parts.This ratio also can be below about 5 quality % of raw material monomer.Perhaps, also can be the raw material monomer that does not contain these monomeric compositions in fact.
An example as the preferred composition of above-mentioned raw material monomer, for except form the property monomer as (methyl) alkyl acrylate of principal monomer and above-mentioned silanol base, also containing the composition of ethene unsaturated monocarboxylic acid, can enumerate and contain the composition of methacrylic acid at least as this ethene unsaturated monocarboxylic acid.The raw material monomer that more preferably contains the composition (being typically the composition that contains AA and MAA but do not contain other ethene unsaturated monocarboxylic acids) of vinylformic acid (AA) and methacrylic acid (MAA) simultaneously.The binder composition that uses the raw material monomer of described composition to obtain can form tackiness (stripping strength etc.), high temperature coherency and terminal preventing property and all excellent tackiness agent of the anti-rebound resilience of foams peeled off.
In containing AA and MAA raw material monomer as mentioned above simultaneously as the composition of ethene unsaturated monocarboxylic acid, the mass ratio of AA and MAA (AA:MAA) for example can be set the scope at about 1:10～about 10:1, preferably sets the scope at about 1:4～about 4:1 usually.From realizing higher high temperature coherency and the anti-elastic viewpoint of foams, preferably make the scope of the mass ratio (AA:MAA) of AA and MAA at about 1:2～about 4:1, for example can be in the scope of about 1:1～about 3:1.
Acrylic polymers as the main component of the binder composition in the technology disclosed herein, be to make above-mentioned raw material monomer polymerization (being typically letex polymerization) and the acrylic polymers that obtains, and the insoluble composition of ethyl acetate shared mass ratio (following be also referred to as sometimes " gel fraction of indicator polymerization thing ") in the These parameters polymkeric substance (Ga) is about 7%～about 17% (for example being about 10%～about 17%).When this Ga is too high, in the tackiness agent or adhesive sheet that are formed by the binder composition based on above-mentioned acrylic polymers (being about to contain the acrylic polymers that the monomeric above-mentioned raw material monomer of silanol base formation property is polymerized under the same conditions), existence is difficult to make tackiness (stripping strength), high temperature compendency and end peel off preventing property with high level and reaches the equilibrated tendency.For example, end is peeled off preventing property and is easily descended sometimes.
Measure above-mentioned " gel fraction of indicator polymerization thing (Ga) " by the following method.
The gel fraction of＜indicator polymerization thing (Ga) measuring method 〉
Will be as the about 0.1g of the indicator polymerization thing (quality: W of working sample A1Mg) the tetrafluoroethylene resin system porous-film (quality: W of usefulness mean pore size 0.2 μ m A2Mg) be bundled into the bundle pocket-like, with sack kite string (quality: W A3Mg) tighten.This pouch is encased in the threaded pipe (1 pouch uses 1 threaded pipe) of capacity 50mL, in this threaded pipe, is full of ethyl acetate.It after room temperature (being typically 23 ℃) is placed 7 days down, is taken out above-mentioned pouch, and drying is 2 hours under 130 ℃, measures the quality (W of this pouch A4Mg).By each is worth the substitution following formula:
Ga[％]＝[(W a4-W a2-W a3)/W a1]×100
Obtain the gel fraction (Ga) of this polymkeric substance.
As above-mentioned tetrafluoroethylene resin system porous-film, preferred use can be from trade(brand)name " ニ ト Off ロ Application (registered trademark) NTF1122 " (mean pore size 0.2 μ m, void content 75%, thickness 0.085mm) or its suitable product of Nitto Denko Corp's acquisition.As the working sample that uses in the said determination, for example can use the water-based emulsion of These parameters polymkeric substance (be typically above-mentioned raw material monomer is removed the silanol base forms that composition behind the property monomer carries out letex polymerization and the water-based emulsion of the polymkeric substance that obtains) at 130 ℃ of samples that obtain after dry 2 hours down.
In addition, as the acrylic polymers of the main component of the binder composition in the technology disclosed herein, the weight-average molecular weight of the solvable composition of its THF (following also abbreviate as sometimes " molecular-weight average ") is (Mw) about 65 * 10 4More than and 100 * 10 4Following scope.When this Mw crosses when being lower than above-mentioned scope, in the tackiness agent or adhesive sheet that form by binder composition, exist to be difficult to make adhesive strength (stripping strength), high temperature coherency and end to peel off preventing property to reach the equilibrated tendency with high level based on this acrylic polymers.For example, the high temperature coherency and terminal peel off in the preventing property any one or the two insufficient easily.On the other hand, when Mw crosses when being higher than above-mentioned scope, there be the Ga tendency more too high of These parameters polymkeric substance than above-mentioned preferable range.In addition, in the tackiness agent or adhesive sheet that are formed by the binder composition based on above-mentioned acrylic polymers, initial stage adhesive strength, binding property (viscosity) have the tendency of decline sometimes.
Measure above-mentioned molecular-weight average (Mw) by the following method.
＜molecular-weight average (Mw) measuring method 〉
To under room temperature (being typically 23 ℃), in THF, flood 7 days as the acrylic polymers of working sample, make the solvable composition stripping of THF.Then, remove by filter the insoluble composition of THF, this filtrate is concentrated as required or dilute (being dissolved in THF again after also can making its drying), preparation is with proper concn (for example about 0.1～about 0.3 quality %.Be 0.2 quality % in embodiment described later) contain the THF solution of the solvable composition of THF.The strainer that is 0.45 μ m with this THF solution mean pore size filters, gained filtrate (sample solution that molecular weight determination is used) is obtained the molecular-weight average of polystyrene standard benchmark by gel permeation chromatography (GPC) device, with the molecular-weight average (Mw) of this value as the solvable composition of THF.As the GPC device, for example can use can be from machine name " the HLC-8120GPC " (chromatographic column: TSKgel GMH-H (S)) of TOSOH Co., Ltd's acquisition.As the working sample that uses in the said determination, for example can use the water-based emulsion of aforesaid propylene acids polymkeric substance at 130 ℃ of dry 2 hours and samples of obtaining down.
Binder composition disclosed herein can be to obtain by above-mentioned raw material monomer (promptly containing the monomeric raw material monomer of silanol base formation property) is carried out letex polymerization, obtaining the acrylic polymers of Mw in the numerical range of afore mentioned rules, and obtain the indicator polymerization thing of Ga in the numerical range of afore mentioned rules.As long as can be met the acrylic polymers of above-mentioned Mw, and be met the indicator polymerization thing of above-mentioned Ga, then above-mentioned emulsion polymeric mode there is not particular restriction, can by with the existing identical mode of known ordinary emulsion polymerization, suitably adopt for example known various monomer supply methods, polymerizing condition (polymerization temperature, polymerization time, polymerization pressure etc.), materials used (polymerization starter, tensio-active agent etc.) to carry out.For example, as the monomer supply method, can adopt whole raw material monomers are disposablely supplied to a feeding mode in the aggregation container, supply with in (droppings) mode, gradation supply (dropping) mode etc. any continuously.Also can be in advance part or all of raw material monomer be mixed with water and emulsification, this emulsion is supplied in the reaction vessel.
As polymerization temperature, can adopt the temperature of for example about 20～about 100 ℃ (being typically about 40～about 80 ℃).As polymerization starter, can illustration: 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-methyl-prop amidine) dithionate, 2,2 '-azo two (2-amidine propane) dihydrochloride, 2,2 '-azo two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, 2,2 '-azo, two (N, N '-dimethylene isobutyl amidine), 2, azo-initiators such as 2 '-azo two [N-(2-propyloic)-2-methyl-prop amidine] hydrate; Persulphate such as Potassium Persulphate, ammonium persulphate; Peroxide initiators such as benzoyl peroxide, tertbutyl peroxide, hydrogen peroxide; Phenyl replaces replacement ethane class initiators such as ethane; Redox class initiators such as the composition of the composition of persulphate and sodium bisulfite, superoxide and sodium ascorbate etc., but be not limited to these.The consumption of polymerization starter with respect to raw material monomer 100 mass parts, for example can be about 0.005～about 1 mass parts.As the supply method of polymerization starter, can adopt the polymerization starter that uses is in fact all put in a feeding mode in the reaction vessel (being typically the aqueous solution of preparing this polymerization starter in reaction vessel), continuous supply formula, the gradation supply mode etc. any before beginning to supply with raw material monomer.From the easiness of converging operation, the viewpoints such as easiness of process management, can preferably adopt for example feeding mode.
As emulsifying agent (tensio-active agent), can use: anionic emulsifier such as sodium lauryl sulphate, ammonium lauryl sulfate, Sodium dodecylbenzene sulfonate, Voranol EP 2001 sodium sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate, polyoxyethylene alkyl phenyl ether sodium sulfate; Nonionic emulsifier such as Voranol EP 2001, polyoxyethylene alkyl phenyl ether etc.Described emulsifying agent can use separately, also can use by composition more than 2 kinds.The consumption of emulsifying agent with respect to raw material monomer 100 mass parts, can be for example about 0.2～about 10 mass parts (preferred about 0.5～about 5 mass parts).
In above-mentioned polymerization (being typically letex polymerization), can use existing known various chain-transfer agents (also can be regarded as molecular weight regulator or polymerization degree conditioning agent) as required.Described chain-transfer agent can be to be selected from for example lauryl mercaptan (dodecyl mercaptans), glycidyl mercaptan, 2 mercapto ethanol, mercaptoacetate, thioglycollic acid-2-ethyl hexyl ester, 2, in 3-dimercapto-thio-alcohols such as 1-propyl alcohol more than a kind or 2 kinds.Wherein, preferably use dodecyl mercaptans.The consumption of chain-transfer agent with respect to raw material monomer 100 mass parts, can be for example about 0.001～about 0.5 mass parts, and this consumption also can be set at about 0.02～about 0.05 mass parts.For example, be about 0.025～about 0.035 mass parts by the consumption that makes chain-transfer agent, can obtain good result.
The mode of described letex polymerization can be set for and make above-mentioned Mw and Ga is in the preferred value scope disclosed herein.(Mw, method Ga) does not have particular restriction to regulating these characteristic values.For example, by the polymerization degree (molecular weight) of suitable setting known effect polymkeric substance or the various factors of molecular structure, the value that can regulate above-mentioned Mw and/or Ga.As the object lesson of available factor in the adjusting of above-mentioned characteristic value, can enumerate: have or not use chain-transfer agent, its kind (compound of use) when using, consumption, the factors relevant such as time supplied with to reaction vessel with chain-transfer agent; The factors relevant such as the kind of polymerization starter (compound of use), consumption, the mode of supplying with to reaction vessel (once, continuously, divide inferior) and service time thereof with polymerization starter; Constitute the monomeric kind of raw material monomer and combination than (for example have or not use above-mentionedly contain the monomer of functional group, its kind when using, this monomer that contains functional group be with respect to the mass ratio of raw material monomer total amount etc.), the supply mode (once, continuously, divide inferior) when reaction vessel is supplied with raw material monomer, the factors relevant such as feed speed when supplying with continuously with raw material monomer; Solid component concentration of polymerization temperature, polymerization time, the water-based emulsion that obtains by polymerization etc.These factors are understood the technology general knowledge that the generality of the influence of Mw or Ga tendency can be used as those skilled in the art, or can easily know by carrying out simple pilot study etc.Set the mode (polymerizing condition) of letex polymerization according to the result of described technology general knowledge and/or pilot study, thus can (Mw Ga) be adjusted to preferred range with above-mentioned characteristic value.
Aqueous adhesive composition disclosed herein is the composition that is scattered in the form in the water based on above-mentioned acrylic polymers and this acrylic polymers.Be meant that at this so-called " based on acrylic polymers " mass ratio shared in the nonvolatile component (solids component) that acrylic polymers contains surpasses 50% in said composition.Also can be that this ratio surpasses 70% binder composition.In addition, shared mass ratio can be in for example about scope of 30～about 80% (being typically about 40～about 70%) in described aqueous adhesive composition for nonvolatile component (solids component).
Binder composition disclosed herein carries out drying and crosslinked (being typically heat cross-linking) with ordinary method, can form tackiness agent (tackiness agent after crosslinked).Being constructed as follows of said composition: mass ratio (following be also referred to as sometimes " gel fraction of tackiness agent ") shared in the tackiness agent of the insoluble composition of ethyl acetate after crosslinked (Gb) is about 20～about 55%.Gb also can be 30～55% (for example about 35～about 55%).Be lower than or cross when being higher than above-mentioned scope when Gb crosses, at this tackiness agent or have in the adhesive sheet of this tackiness agent, exist to be difficult to make adhesive strength (stripping strength), high temperature coherency and end to peel off preventing property to reach the equilibrated tendency with high level.For example, when Gb crosses when low, the high temperature coherency is not enough easily, and when Gb was too high, end was peeled off preventing property and descended easily.
Measure above-mentioned " gel fraction of tackiness agent (Gb) " by the following method.
The gel fraction of＜tackiness agent (Gb) measuring method 〉
Peeling off adhesive bonding agent composition (being typically coating) on the liner.It was descended dry 2 minutes at 100 ℃,, again it was preserved 3 days under 50 ℃ environment at the above-mentioned binder layer that forms the about 50 μ m of thickness～about 100 μ m on the liner of peeling off.Afterwards, gather about 0.1g (quality: W from this binder layer B1Mg) adhesive sample is the tetrafluoroethylene resin system porous-film (quality: W of 0.2 μ m with mean pore size with it B2Mg) be bundled into the bundle pocket-like, with sack kite string (quality: W B3Mg) tighten.This pouch is packed in the threaded pipe (1 pouch with 1 threaded pipe) of capacity 50mL, in this threaded pipe, be full of ethyl acetate.It after room temperature (being typically 23 ℃) is placed 7 days down, is taken out above-mentioned pouch, and drying is 2 hours under 130 ℃, measures the quality (W of this pouch B4Mg).By each is worth the substitution following formula:
Gb[％]＝[(W b4-W b2-W b3)/W b1]×100
Obtain the gel fraction (Gb) of tackiness agent.
As above-mentioned tetrafluoroethylene resin system porous-film, preferably use above-mentioned trade(brand)name " ニ ト Off ロ Application (registered trademark) NTF1122 " or its suitable product.
Preferably the copolymerization composition of aforesaid propylene acids polymkeric substance etc. being set for makes above-mentioned gel fraction (Gb) in the preferable range disclosed herein.For example, form by the silanol base in the raw material monomer that will in the manufacturing of acrylic polymers, use that property is monomeric to contain proportional being set in the above-mentioned preferred range, can obtain having the binder composition of above-mentioned preferred Gb.
By only containing in the binder composition that the raw material monomer of forming of vinylformic acid as the ethene unsaturated monocarboxylic acid obtain, above-mentioned gel fraction (Gb) is preferably about 35%～about 55% (more preferably about 40%～about 50%).By only contain methacrylic acid as the ethene unsaturated monocarboxylic acid or contain vinylformic acid and binder composition that the raw material monomer of forming of methacrylic acid (being typically the ethene unsaturated monocarboxylic acid that does not contain beyond vinylformic acid and the methacrylic acid) obtains in, Gb is preferably about 20%～about 45% (more preferably about 25%～about 40%, more preferably about 30%～about 40%).If adopt the tackiness agent satisfy described Gb, then can higher level realize balancedly that tackiness, high temperature coherency and end peel off these 3 characteristics of preventing property (also comprising anti-elastic 4 characteristics of foams).
In addition, acrylic polymers as the main component of the binder composition in the technology disclosed herein, be preferably as follows measure the insoluble composition of ethyl acetate obtain mass ratio (following be also referred to as sometimes " gel fraction of acrylic polymers ") (Gc) in about scope of 20%～about 55%, more preferably in about scope of 35%～about 45%.With the acrylic polymers that satisfies described Gc is the binder composition of main component, can form with higher level and realize that balancedly tackiness, high temperature coherency and end peel off these 3 characteristics of preventing property tackiness agent of (also comprising anti-elastic 4 characteristics of foams).
The gel fraction of＜acrylic polymers (Gc) measuring method 〉
Will be as the about 0.1g of the acrylic polymers of working sample (quality: W C2Mg) with mean pore size be the tetrafluoroethylene resin system porous-film (quality: W of 0.2 μ m C2Mg) be bundled into the bundle pocket-like, with sack kite string (quality: W C3Mg) tighten.This pouch is encased in the threaded pipe (1 pouch with 1 threaded pipe) of capacity 50mL, in this threaded pipe, is full of ethyl acetate.It after room temperature (being typically 23 ℃) is placed 7 days down, is taken out above-mentioned pouch, and drying is 2 hours under 130 ℃, measures the quality (W of this pouch C4Mg).By each is worth the substitution following formula:
Gc[％]＝[(W c4-W c2-W c3)/W c1]×100
Obtain the gel fraction (Gc) of acrylic polymers.
As above-mentioned tetrafluoroethylene resin system porous film, preferably use above-mentioned trade(brand)name " ニ ト Off ロ Application (registered trademark) NTF1122 " or its suitable product.In addition, as being used for the working sample that said determination is used, for example can use the water-based emulsion of acrylic polymers at 130 ℃ of samples that obtain after dry 2 hours down.
As long as not obvious infringement effect of the present invention, then can in above-mentioned binder composition, append and cooperate the linking agent that is selected from for example hydrazine class linking agent, epoxies linking agent, carbodiimide class linking agent, isocyanates linking agent, oxazoline class linking agent, aziridines linking agent, metallo-chelate class linking agent, the silane coupling agent etc.These linking agents can use separately or be used in combination more than 2 kinds.Perhaps, also can be the binder composition of mismatching the composition of described linking agent.
Do not have particular restriction, but the weight-average molecular weight (Mx) of the solvable composition of THF of above-mentioned tackiness agent after crosslinked for example can be about 10 * 10 in the polystyrene standard benchmark 4～about 80 * 10 4(preferred about 20 * 10 4～about 60 * 10 4).This Mx can measure by the method identical with the weight-average molecular weight (Mw) of the solvable composition of THF of aforesaid propylene acids polymkeric substance.When Mx crosses when being lower than above-mentioned scope, at this tackiness agent or have in the adhesive sheet of this tackiness agent, tackiness (binding property, for example stripping strength), high temperature coherency and the terminal balance of peeling off between the preventing property are destroyed easily sometimes.For example, the high temperature coherency is not enough easily.On the other hand, cross in the tackiness agent that is higher than above-mentioned scope at Mx, initial stage adhesive strength, binding property (viscosity) have the tendency of decline.This Mx can be for example uses chain-transfer agent according to having or not when making acrylic polymers, when using chain-transfer agent its kind (compound of use) and consumption, silanol base form the monomeric kind of property, silanol base form the property monomer with respect to the mass ratio of raw material monomer total amount, have or not use the monomer that contains functional group, its kind, this monomer that contains functional group are regulated with respect to the factors such as mass ratio of raw material monomer total amount when using the monomer that contains functional group.
In one of optimal way of binder composition disclosed herein, said composition also contains tackifier.As described tackifier, can use in the various tackifier resins such as for example being selected from rosin based resin, rosin derivative resin, petroleum resinoid, terpenoid resin, phenolic resin, ketone resin more than a kind or 2 kinds.As described rosin based resin, for example except rosin such as gum resin, wood rosin, toll oil rosin, also can enumerate: stabilization rosin (for example above-mentioned rosin is carried out homogenizing not or hydrotreatment and obtain stabilization rosin), polymerized rosin (for example above-mentioned rosiny polymer, be typically dipolymer), modified rosin (for example the unsaturated acid modified rosin by unsaturated acid modifications such as toxilic acid, fumaric acid, (methyl) vinylformic acid etc.) etc.As above-mentioned rosin derivative resin, can enumerate: the resinoid carboxylate of above-mentioned rosin, phenol-modified thing and carboxylate thereof etc.As above-mentioned petroleum resinoid, can illustration: aliphatic category petroleum resin, fragrant same clan petroleum resin, copolymerization class petroleum resin, alicyclic ring same clan petroleum resin, their hydride etc.As above-mentioned terpenoid resin, can enumerate: α-Pai Xishuzhi, beta-pinene resin, aromatic series modification terpenoid resin, terpenes phenol resin etc.As above-mentioned ketone resin, for example can enumerate: by ketone (aliphatic ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl phenyl ketone for example; Alicyclic ketone such as pimelinketone, methylcyclohexanone etc.) ketone resin that obtains with the condensation of formaldehyde.
From improving coherent viewpoint under the hot environment etc., for example can preferably adopting, softening temperature is about the tackifier that (are typically 140～180 ℃) more than 140 ℃.As the commercially available product of tackifier with described softening temperature, can illustration: trade(brand)name " ス-パ-エ ス テ Le E-865 ", " ス-パ-エ ス テ Le E-865NT ", " ス-パ-エ ス テ Le E-650 ", " ス-パ-エ ス テ Le E-786-60 ", " タ マ ノ Le E-100 ", " タ マ ノ Le E-200 ", " タ マ ノ Le 803L ", " ペ Application セ Le D-160 ", " the ペ Application セ Le KK " that can obtain from Arakawa Chemical Industries, Ltd.; The trade(brand)name " YS ボ リ ス タ-S " that can obtain from ヤ ス Ha ラ ケ ミ カ Le Co., Ltd., " YS ボ リ ス タ-T ", " マ イ テ イ エ-ス G " etc.; But be not limited to these.By adopting softening temperature to be about the tackifier that (are typically 160～180 ℃) more than 160 ℃, can provide the binder composition of the more high performance binder layer of formation.For example, can provide coherency and other characteristics (stripping strength, end are peeled off preventing property etc.) under the hot environment to reach the equilibrated binder composition with higher level.Above-mentioned tackifier can only use a kind, also can be used in combination more than 2 kinds.
Described tackifier typical case adds in the water-based emulsion of acrylic polymers and uses.The addition manner of tackifier does not have particular determination.Usually, the form that is fit to be scattered in these tackifier the aqueous dispersions (tackifier emulsion) in the water is added.
The cooperation ratio of tackifier is a benchmark with nonvolatile component (solids component), for example can be set at below about 50 mass parts with respect to acrylic polymers 100 mass parts.Usually, suit above-mentioned cooperation ratio is about below 40 mass parts.The lower limit of tackifier levels does not have particular restriction, is set at more than about 1 mass parts with respect to acrylic polymers 100 mass parts usually, obtains good result thus.In one of optimal way of binder composition disclosed herein, the cooperation ratio (containing proportional) that makes these tackifier is counted about 5～about 40 mass parts (be typically about 5～about 30 mass parts, for example be about 15～about 30 mass parts) with respect to acrylic polymers 100 mass parts with the solids component benchmark.If adopt the binder composition that uses tackifier with described ratio, then with the crosslinked tackiness agent that forms of the mode that forms above-mentioned preferred Gb or have in the adhesive sheet of this tackiness agent, can realize that balancedly coherency and end under tackiness (stripping strength), the hot environment peel off these 3 characteristics of preventing property with higher level.
Binder composition disclosed herein can contain any composition of component of polymer conduct beyond the aforesaid propylene acids polymkeric substance.As described component of polymer, the polymkeric substance that preferably has rubber or elastomeric character, can illustration for example: vinyl-vinyl acetate copolymer, acrylic rubber, natural rubber (NR), synthetic polyisoprene (IR), styrene butadiene ribber (SBR), chloroprene rubber (CR), isoprene-isobutylene rubber (IIR), ethylene propylene rubber (EPM, EPDM), polyisobutene, styrene-ethylene-butylene-styrene multipolymer (SEBS), acrylonitrile butadiene copolymer (NBR), styrene-butadiene-styrene block copolymer (SBS), styrene isoprene styrene block copolymer (SIS) (SIS), polyvinyl alkyl oxide (for example polyvinyl isobutyl ether) etc.Can use a kind in them separately or will be used in combination more than 2 kinds.
Above-mentioned component of polymer for example is scattered in the water-based emulsion that emulsion form in the water is coupled to aforesaid propylene acids polymkeric substance with this component of polymer and uses.The content of this component of polymer (cooperation ratio) is benchmark with nonvolatile component (solids component), is suitably usually below about 50 mass parts with respect to acrylic polymers 100 mass parts (for example to be about 5～about 50 mass parts).The cooperation ratio that also can make described component of polymer is below 5 mass parts, also can be the binder composition that does not contain the composition of this component of polymer in fact.
Binder composition disclosed herein can contain and is useful on acid or the alkali (ammoniacal liquor etc.) of regulating pH etc.As other any compositions that can in said composition, contain, can illustration: common various additives in the aqueous adhesive composition field such as tinting materials such as viscosity modifier, levelling agent, softening agent, weighting agent, pigment, dyestuff, stablizer, sanitas, antiaging agent.About above-mentioned additive, can utilize ordinary method to use existing known material, owing to be not feature of the present invention, so detailed.
Adhesive sheet of the present invention has the binder layer that uses any binder composition disclosed herein and form.Can be the adhesive sheet of tape base material that has the form of described binder layer on the single or double of flat substrates (supporter), perhaps can be to peel off the adhesive sheet of no base material that liner is provided with the form etc. of this binder layer.In the notion of this so-called adhesive sheet, can comprise the adhesive sheet that is called as self adhesive tape, adhesive label, bonding film etc.In addition, above-mentioned binder layer is not limited to the binder layer that forms continuously, also can be the binder layer that for example forms rule such as point-like, strip or random patterns.
Adhesive sheet disclosed herein can have for example Fig. 1～cross section structure shown in Figure 6.Wherein, Fig. 1, Fig. 2 are the configuration examples of adhesive sheet of the tape base material of both-sided adhesive type.Adhesive sheet 11 shown in Figure 1 has following formation: on base material 1 two-sided binder layer 2 is set, these binder layers 2 are that the liner 3 of peeling off of release surface is protected respectively by this binder layer side at least.Adhesive sheet 12 shown in Figure 2 has following formation: on base material 1 two-sided binder layer 2 is set, in these binder layers one peels off liner 3 protections by two-sided for release surface.This adhesive sheet 12 can become following formation: by this adhesive sheet 12 of reeling another binder layer is contacted with the back side of peeling off liner 3, make this another binder layer also by peeling off liner 3 protections.
Fig. 3, Fig. 4 are the configuration examples of the self adhesive tape of no base material.Adhesive sheet 13 shown in Figure 3 has following formation: the two-sided of the binder layer 2 of no base material is that the liner 3 of peeling off of release surface is protected respectively by this binder layer side at least.Adhesive sheet 14 shown in Figure 4 has following formation: a face of the binder layer 2 of no base material is protected by the two-sided liner 3 of peeling off for release surface; it also can become following formation: when it is reeled; another face of binder layer 2 is contacted with peeling off liner 3, and this another face is also by peeling off liner 3 protections.
Fig. 5, Fig. 6 are the configuration examples of adhesive sheet of the tape base material of single face adhesion type.Adhesive sheet 15 shown in Figure 5 has following formation: binder layer 2 is set on the single face of base material 1, and the surface of this binder layer 2 (gluing surface) is that the liner 3 of peeling off of release surface is protected by this binder layer side at least.Adhesive sheet 16 shown in Figure 6 has the formation that binder layer 2 is set on a face of base material 1.It also can become following formation: another face of this base material 1 is a release surface, if adhesive sheet 16 is reeled, then this another face contacts with binder layer 2, and the surface of this binder layer (gluing surface) is by another face protection of base material 1.
As the base material that constitutes above-mentioned adhesive sheet, can suitably select for example to use according to the purposes of adhesive sheet: plastic films such as polypropylene screen, ethylene-propylene copolymer film, polyester film, polychloroethylene film; Foam substrate such as urethane foam, polyethylene foam; Paper such as kraft paper, crepe paper, Japan paper; Cloth such as cotton, staple fibre cloth; Non-woven fabrics such as polyester non-woven fabric, vinylon non-woven fabrics; Tinsel such as aluminium foil, Copper Foil etc.As above-mentioned plastic film, can use in unstretching film and stretching (uniaxial extension or the biaxial stretch-formed) film any.In addition, can carry out the surface treatment such as coating, Corona discharge Treatment of priming paint to the face that is provided with binder layer in the base material.The thickness of base material can suitably be selected according to purpose, but is generally about 10 μ m～about 500 μ m (being typically 10 μ m～200 μ m).
Above-mentioned binder layer for example can be by adhering to any aqueous adhesive composition disclosed herein (being typically coating) at base material or peel off on the liner and the said composition drying is formed.The coating of binder composition can be used intaglio plate roll coater for example, contrary roll coater, roller to lick coating machines commonly used such as formula coating machine, dipping roll coater, metering bar coater, knife coater, spraying machine and carry out.The coating thickness of binder composition does not have particular restriction, but can make the thickness of the binder layer of dry back formation for example be the coating thickness of about 2 μ m～about 150 μ m (being typically about 5 μ m～about 100 μ m).From viewpoint such as promote crosslinking reaction, enhance productivity, preferably under heating, carry out the drying of binder composition.Though according to the kind of base material and different, can adopt for example about 40～about 120 ℃ drying temperature.In addition, under the situation of the adhesive sheet of tape base material, can be on base material directly adhesive bonding agent composition form binder layer, also can be transferred on the base material peeling off the binder layer that forms on the liner.
According to adhesive sheet provided by the invention can be the high-performance adhesive sheet of realizing multifrequency nature with high level simultaneously.For example be to realize balancedly that with higher level tackiness (stripping strength etc.), coherency (the particularly coherency under the hot environment) and end peel off the adhesive sheet of these 3 characteristics of preventing property (curved surface tackiness).At this, the cohesive force under the hot environment can be learnt by the confining force (heat-resisting confining force) under 80 ℃ of the mensuration described later.In addition, above-mentioned end is peeled off preventing property and be can be used as the index of expression to the tackiness (carrying out gluing performance along the surface shape that is attached body) of the curved surface of adhesive sheet etc., for example can test by terminal separability described later and learn.
According to adhesive sheet provided by the invention, can be except above-mentioned 3 characteristics, also to realize the anti-elastic high-performance adhesive sheet of foams with high level simultaneously.The anti-rebound resilience of these foams is the character that can be used as the index of the uneven surface tackiness of representing adhesive sheet, for example can the crooked anti-resiliency test of foams that attaches of foams base material be learnt by aftermentioned.
The reason that reaches above-mentioned excellent effect is still indeterminate, but is speculated as for example as described below.That is constituting of binder composition disclosed herein: to satisfy molecular-weight average (Mw) 65 * 10 4～100 * 10 4And the gel fraction of These parameters polymkeric substance (Ga) is that the acrylic polymers below 7%～17% is a main body, and to be formed on crosslinked back gel fraction (Gb) be 20%～55% tackiness agent.The gel fraction of These parameters polymkeric substance (Ga) can be peeled off the generation of preventing property to the end of the tackiness agent that obtained by this binder composition or adhesive sheet to be influenced greatly.In addition, the molecular-weight average of aforesaid propylene acids polymkeric substance (Mw) and crosslinked after the gel fraction (Gb) of tackiness agent can peel off the generation of preventing property to high temperature coherency and end and influence greatly.Satisfy above-mentioned Ga, Mw and the whole binder composition of Gb if adopt, then can when guaranteeing required tackiness, improve the high temperature coherency and end is peeled off preventing property, realize thus forming the well balanced tackiness agent of above-mentioned 3 characteristics or the binder composition of adhesive sheet.
Embodiment
Below, several embodiment that the present invention is correlated with are described, but are not to attempt the present invention is defined in these specific embodiments.Need to prove that " part " reaches " % " in below illustrating is not having to be quality standard under the special situation about illustrating.
In addition, the molecular-weight average (Mw) of the solvable composition of THF of acrylic polymers, for molecular weight determination sample solution with method for preparing, use can be installed from the gel permeation chromatography (GPC) that TOSOH Co., Ltd obtains, machine name " HLC-8120GPC ", under following condition, measure, obtain the weight-average molecular weight of polystyrene benchmark.
[GPC condition determination]
Sample size: 10 μ L (the THF solution of concentration 0.2 quality %)
Elutriant: THF
Flow velocity: 0.6mL/ branch
Measure temperature: 40 ℃
Chromatographic column: TSKgel GMH-H (S)
Detector: differential refractometer
＜example 1 〉
Take into account in the reaction vessel of stirrer having cooling tube, nitrogen ingress pipe, temperature, drop into 2,35 parts of 0.1 part in two [N-(2-propyloic)-2-methyl-prop amidine] hydrates (polymerization starter) of 2 '-azo (trade(brand)name " VA-057 " that use can obtain from Wako Pure Chemical Industries, Ltd.) and ion exchanged waters stirred 1 hour when importing nitrogen.Hold it under 60 ℃, be added with 30 parts of butyl acrylates with 3 hours to wherein slowly dripping in 40 parts of ion exchanged waters, 70 parts of ethyl acrylates, 4 parts in vinylformic acid (AA), form 0.02 part of the monomeric 3-methacryloxypropyl trimethoxy silane of property (trade(brand)name " KBM-503 " that use can obtain from Shin-Etsu Chemial Co., Ltd) as the silanol base, the emulsification that 0.033 part of dodecyl mercaptans (chain-transfer agent) and dodecyl polyoxyethylene sodium sulfate (emulsifying agent) are 2 parts (promptly, the emulsion of raw material monomer), make it carry out the emulsion polymerization reaction.After the raw material monomer emulsion drips end, under same temperature, keep making in 3 hours its slaking again.Add 10% ammoniacal liquor therein the pH of liquid is transferred to 7.5.Thus, obtain the aqueous dispersions (emulsion) of acrylic polymers.Below, sometimes this acrylic polymer emulsions is called " emulsion E1 ".The molecular-weight average (Mw) that constitutes the acrylic polymers of this emulsion E1 is measured under these conditions.
On the other hand, prepare the emulsion of above-mentioned raw material monomer from the raw material monomer of above-mentioned use, to remove composition after the 3-methacryloxypropyl trimethoxy silane (silanol base form property monomer), in addition, identical with the making of above-mentioned emulsion E1, obtain the aqueous dispersions (emulsion) of the indicator polymerization thing corresponding with the acrylic polymers that constitutes this emulsion E1.For the indicator polymerization thing that constitutes this emulsion, use mass ratio (gel fraction) that aforesaid method measures the insoluble composition of ethyl acetate (Ga).
In above-mentioned emulsion E1, with the per 100 parts of emulsions of adding 20 parts of (is benchmark with the solids component) tackifier of the acrylic polymers that contains in this emulsion (aqueous dispersions of the polymerized rosin resin that trade(brand)name " ス-バ-エ ス テ Le E-865NT ", the softening temperature that can obtain from Arakawa Chemical Industries, Ltd. is 160 ℃), obtain the binder composition of example 1.
Handling the resulting above-mentioned binder composition of coating of peeling off on the liner of high-quality paper with the silicone stripper.With its 100 ℃ dry 2 minutes down, peel off the binder layer that forms the about 70 μ m of thickness on the liner at this, thereby obtain the adhesive sheet of the no base material that forms by this binder layer.The adhesive sheet of this no base material preserving 3 days after the making, is gathered adhesive sample from this adhesive sheet then under 50 ℃ environment, measure the shared mass ratio (gel fraction) of the insoluble composition of ethyl acetate in the tackiness agent after crosslinked (Gb) by aforesaid method.
In addition, use above-mentioned binder composition to make with the double-sided adhesive sheet of non-woven fabrics as base material.Promptly, prepare 2 with the above-mentioned sample of peeling off on the liner binder layer that forms the about 70 μ m of thickness that operates in equally, they are attached on non-woven fabrics (can from big clear and the non-woven fabrics that paperboard Co., Ltd. obtains of Japan, trade(brand)name " the concise paper of using ") two-sided, obtain double-sided adhesive sheet.Two adhesive faces of this double-sided adhesive sheet are directly peeled off liner protection by what use in the making of this adhesive sheet.
＜example 2 〉
In the raw material monomer that example 1 is used, the consumption of 3-methacryloxypropyl trimethoxy silane is changed to 0.015 part, the consumption of dodecyl mercaptans is changed to 0.03 part.All operate equally with example 1 other aspects, obtains acrylic polymer emulsions (below be sometimes referred to as " emulsion E2 ").In above-mentioned emulsion E2, with same ratio add with example 1 in the identical tackifier emulsion of tackifier emulsion of use, obtain the binder composition of example 2.Use this binder composition to make double-sided adhesive sheet by the method identical with example 1.
＜example 3 〉
Use the raw material monomer of the composition identical, but in example 1, spend the emulsion that dripped this raw material monomer in 3 hours, drip this emulsion and spend 4 hours in this example with example 1.All operate equally with example 1 other aspects, obtains acrylic polymer emulsions (below be sometimes referred to as " emulsion E3 ").In above-mentioned emulsion E3, add the tackifier emulsion identical with same ratio with example 1, obtain the binder composition of example 3.Use this binder composition to make double-sided adhesive sheet by the method identical with example 1.
＜example 4 〉
In the raw material monomer that example 1 is used, the consumption of 3-methacryloxypropyl trimethoxy silane is changed to 0.04 part, the consumption of dodecyl mercaptans is changed to 0.036 part.Other aspects and example 1 are operated equally, obtain acrylic polymer emulsions (below be sometimes referred to as " emulsion E4 ").In above-mentioned emulsion E4, add the tackifier emulsion identical with same ratio with example 1, obtain the binder composition of example 4.Use this binder composition to make double-sided adhesive sheet by the method identical with example 1.
＜example 5 〉
In the raw material monomer that example 1 is used, the consumption of 3-methacryloxypropyl trimethoxy silane is changed to 0.06 part, the consumption of dodecyl mercaptans is changed to 0.036 part.Other aspects and example 1 are operated equally, obtain acrylic polymer emulsions (below be sometimes referred to as " emulsion E5 ").In this emulsion E5, add the tackifier emulsion identical with same ratio with example 1, obtain the binder composition of example 5.Use this binder composition to make double-sided adhesive sheet by the method identical with example 1.
For the acrylic polymers that constitutes above-mentioned each acrylic polymer emulsions E2～E5, similarly measure Mw with example 1.In addition,, similarly make emulsion with the corresponding indicator polymerization thing of the acrylic polymers that constitutes each emulsion, obtain the Ga of this indicator polymerization thing with example 1 at above-mentioned each emulsion E2～E5.At this moment, in the making of the indicator polymerization thing corresponding, be set at 4 hours equally with removing dropping time and the emulsion E3 that the silanol base forms the raw material monomer emulsion of the composition behind the property monomer with emulsion E3.In addition, similarly measure the gel fraction (Gb) of the tackiness agent that each binder composition by example 2～example 5 obtains with example 1.
The double-sided adhesive sheet that makes in example 1～example 5 after preserving 3 days after the making, carrying out slaking, is estimated following characteristic under 50 ℃ environment.
[stripping strength mensuration]
The liner of peeling off that covers a face of double-sided adhesive sheet is peeled off, binder layer is exposed, it is attached on the PET film of thick 25 μ m pastes lining.Adhesive sheet behind this subsides lining is cut into the size of wide 20mm, long 100mm, making test film.To peel off liner from another face of above-mentioned test film and peel off, the method that comes and goes 1 time by the roller that makes 2kg is crimped on this test film as on the SUS304 stainless steel plate that is attached body.With its 23 ℃ down place 30 minutes after, according to JIS Z0237, under the mensuration environment of 23 ℃ of temperature, relative humidity 50%, use tensile testing machine under the condition of 180 ° of draw speed 300mm/ branches, peel angle, to measure stripping strength (N/20mm is wide).
[test of high temperature coherency]
The liner of peeling off that covers a face of double-sided adhesive sheet is peeled off, binder layer is exposed, it is attached on the PET film of thick 25 μ m pastes lining.Adhesive sheet behind this subsides lining is cut into the size of wide 10mm, long 100mm, making test film.To peel off liner from another face of above-mentioned test film and peel off, and come and go 1 time method with the gluing area of wide 10mm, long 20mm by the roller that makes 2kg this test film is crimped on as on the hard rubber sheet that is attached body.With this hard rubber sheet in sagging placement under 80 ℃ the environment after 30 minutes, apply the load of 500g at the free end of test film, according to JIS Z0237, be determined under the state that has applied this load the size (distance) of the skew of test film after placing 1 hour under 80 ℃ the environment.
[terminal stripping test]
The liner of peeling off that covers a face of double-sided adhesive sheet is peeled off, binder layer is exposed, it is attached on the aluminium sheet of thick 0.5mm, wide 10mm, long 90mm, make test film.After the length direction of this test film bent to arcuation along the pole of φ 50mm, will peel off liner from another face of this test film and peel off, and use laminating machine to be crimped on the polypropylene board.It was placed 24 hours under 23 ℃ environment, after 2 hours, measure the height (mm) of the test film end of floating in heating under 70 ℃ then from the polypropylene board surface.
The kind of the emulsion of using in the preparation of the binder composition of example 1～example 5, constitute this emulsion acrylic polymers the solvable composition of THF molecular-weight average (Mw), the indicator polymerization thing corresponding with this acrylic polymers the insoluble composition of ethyl acetate mass ratio (Ga) and crosslinked after the mass ratio (Gb) of the insoluble composition of ethyl acetate of tackiness agent and the result of above-mentioned evaluation test as shown in table 1.
Table 1
Emulsion Mw(×10 4) Ga(％) Gb(％) Stripping strength [N/20mm] Coherency [mm/hr] End is peeled off [mm]
Example 1 E1 86.8 14.0 41.3 13.3 1.1 1.3
Example 2 E2 92.6 12.0 41.4 14.3 0.9 0.9
Example 3 E3 67.1 16.0 48.0 14.4 0.9 0.4
Example 4 E4 62.1 7.2 44.7 14.1 0.6 14.8
Example 5 E5 44.7 7.2 49.8 13.8 0.4 15.2
As shown in table 1, having use is 65 * 10 with Mw 4～100 * 10 4And the Ga of indicator polymerization thing is that the acrylic polymers of 7%～17% (more specifically being 10%～17%) is that Gb that the binder composition of main body forms is 20～55% (more specifically to be 30%～55%, and then be 35%～50%, be in particular 40%～50%) the adhesive sheet of example 1～3 of binder layer, all demonstrate the stripping strength of 12N/20mm above (and then for more than 13N/20mm), that does not find test film in high temperature coherency test drops midway that (bias size after other 1 hour is below the 2.5mm, particularly 1.5mm is following), peeling off in the terminal stripping test highly is 2mm following (and then for below 1.5mm).That is be that tackiness, high temperature coherency and the terminal adhesive sheet of peeling off preventing property are realized in high balance ground.
Relative therewith, though the stripping strength of the adhesive sheet of example 4,5 and high temperature coherency are roughly the same with example 1～3, end is peeled off preventing property variation significantly.That is, compare lack of balance between above-mentioned 3 characteristics (tackiness, high temperature coherency and end are peeled off preventing property) with the adhesive sheet of example 1～3.
In addition, binder composition disclosed herein can form through the time change (for example Gb, tackiness, high temperature coherency and terminal peel off the characteristic more than a kind or 2 kinds in the preventing property through the time change) few tackiness agent and the adhesive sheet that possesses this tackiness agent.Support that the embodiment of this content is as follows.
That is, with the adhesive sheet of the no base material of example 1 and double-sided adhesive sheet after the making after preserving 7 days under 70 ℃ the environment, with above-mentionedly carry out equally that Gb, stripping strength measure, the test of high temperature coherency and the test of terminal separability.Consequently, stripping strength, high temperature coherency and terminal the preventing property of peeling off are all kept performance with the result shown in the table 1 (result who uses the adhesive sheet after preserving 3 days under 50 ℃ the environment to estimate) equal extent, also do not see the decline of Gb in addition.
＜example 6 〉
Use the raw material monomer of the composition identical, operate equally, obtain the emulsion (below be also referred to as " emulsion E6 ") of acrylic polymers with example 1 with example 1.In this emulsion E6 with same ratio add with example 1 in the identical tackifier emulsion of tackifier emulsion of use, obtain the binder composition of example 6.Use said composition to make double-sided adhesive sheet by the method identical with example 1.
＜example 7 〉
In the raw material monomer that example 1 is used, use AA3 part and methacrylic acid (MAA) to replace AA4 part for 1 part.Other aspects and example 1 are operated equally, obtain acrylic polymer emulsions (below be also referred to as " emulsion E7 ").In this emulsion E7 with same ratio add with example 1 in the identical tackifier emulsion of tackifier emulsion of use, obtain the binder composition of example 7.Use said composition to make double-sided adhesive sheet by the method identical with example 1.
＜example 8 〉
Except using AA2 part and MAA2 part to replace operating equally with example 1 AA4 part, obtain acrylic polymer emulsions (below be also referred to as " emulsion E8 ").In this emulsion E8 with same ratio add with example 1 in the identical tackifier emulsion of tackifier emulsion of use, obtain the binder composition of example 8.Use said composition to make double-sided adhesive sheet by the method identical with example 1.
＜example 9 〉
Except using AA1 part and MAA3 part to replace operating equally with example 1 AA4 part, obtain acrylic polymer emulsions (below be also referred to as " emulsion E9 ").In this emulsion E9 with same ratio add with example 1 in the identical tackifier emulsion of tackifier emulsion of use, obtain the binder composition of example 9.Use said composition to make double-sided adhesive sheet by the method identical with example 1.
To constituting the acrylic polymers of above-mentioned each acrylic polymer emulsions E6～E9, the mass ratio (gel fraction) of measuring Mw and the insoluble composition of ethyl acetate by aforesaid method (Gc).In addition, similarly measure the gel fraction (Gb) of the tackiness agent that each binder composition by example 6～example 9 obtains with example 1.The measurement result of above-mentioned Mw, Gc and Gb is as shown in table 2.Show simultaneously in this table 2: the kind of the acrylic polymer emulsions of using in the preparation of the binder composition of example 6～example 9 and the vinylformic acid that raw material monomer contained that in each emulsion is made, uses and the amount of methacrylic acid.In addition, for above-mentioned each emulsion E6～E9, similarly make emulsion with the corresponding indicator polymerization thing of the acrylic polymers that constitutes each emulsion with example 1, obtain the gel fraction (Ga) of these indicator polymerization things, result's indicator polymerization thing arbitrarily is about 14%.
Table 2
Emulsion AA (part) MAA (part) Mw(×10 4) Gc(％) Gb(％)
Example 6 E6 4 0 78.2 39.7 43.8
Example 7 E7 3 1 74.3 39.6 38.6
Example 8 E8 2 2 77.0 40.1 37.7
Example 9 E9 1 3 79.6 36.2 24.8
With the double-sided adhesive sheet that makes in example 6～example 9 after the making in preserve under 50 ℃ the environment carried out slaking in 3 days after, use this double-sided adhesive sheet and above-mentioned stripping strength, high temperature coherency and the end similarly estimated to peel off.In addition, use above-mentioned double-sided adhesive sheet to come the anti-rebound resilience of assess foam body by following method.Its result is as shown in table 3.
[the anti-resiliency test of foams]
The liner of peeling off that covers a face of double-sided adhesive sheet is peeled off, binder layer is exposed, and make on its urethane foam that fits to thick 10mm (trade(brand)name " ECS Off オ-system " that can obtain from イ ノ ア Star Network Co., Ltd.) with the hand roller, it is cut into wide 10mm, long 50mm makes test film.To peel off liner from another face of this test film peels off, binder layer is exposed, the gluing surface of above-mentioned test film with wide 10mm, long 10mm overstock on the face of the acrylonitrile-butadiene-styrene copolymer resin board (ABS plate) that is connected to thick 2mm with 2kg roller round trip.Then, the rest part (wide 10mm, long 40mm) with this test film bends and fits on another face of ABS plate.It was placed 24 hours under 23 ℃ environment, again after placing 2 hours under 70 ℃ the environment, measure in the above-mentioned face side (gluing area is the side of wide 10mm, long 10mm) height (mm) of the end of the test film that floats from the ABS plate.
Table 3
Stripping strength [N/20mm] Coherency [mm/hr] End is peeled off [mm] The anti-rebound resilience of foams [mm]
Example 6 13.4 0.9 0.3 10.0
Example 7 12.5 1.4 0.1 0.9
Example 8 12.9 1.9 0.1 1.2
Example 9 13.1 2.5 0.3 1.4
As shown in table 3, the adhesive sheet of example 6～example 9 all demonstrates the stripping strength of 12N/20mm above (further for more than the 12.5mm), do not see dropping of test film midway in the test of high temperature coherency, peeling off in the stripping test highly is 2mm following (further following for 0.5mm) endways.That is, peel off these 3 characteristics of preventing property with balance realization tackiness, high temperature coherency and the end of height.In addition, with compare by the adhesive sheet that only contains the example 6 that the raw material monomer of AA as the ethene unsaturated monocarboxylic acid obtain, use at the same time in AA and the MAA adhesive sheet as the example 7～example 9 of ethene unsaturated monocarboxylic acid, the anti-rebound resilience of foams significantly improves.Particularly, the adhesive sheet of example 7～example 9 peeling off in the anti-resiliency test of foams highly all at (further for below the 2mm) below the 5mm.As mentioned above, the adhesive sheet of example 7～example 9 is all peeled off preventing property and these 4 characteristics of the anti-rebound resilience of foams with high-level equilibrium ground realization tackiness, high temperature coherency, end.In addition, also using in the example of AA and MAA, constant and make the example 7～9 that changes in the scope of mass ratio of AA:MAA (promptly at total consumption of AA and MAA at 3:1～1:3, adhesive sheet with the identical tackiness agent of condition the mass ratio of AA:MAA in raw material monomer) in, observes along with AA:MAA increases the tendency that high temperature coherency and the anti-rebound resilience of foams improve.In the quality of AA:MAA is to obtain good especially result in the example 7 of 1:1～3:1 and the example 8.
＜example 10 〉
The raw material monomer of use and example 9 same compositions, but in example 9, spend the emulsion that dripped this raw material monomer in 3 hours, drip this emulsion and spend 4 hours in this example.All operate equally with example 1 other aspects, obtains acrylic polymer emulsions (below be also referred to as " emulsion E10 ").In this emulsion E10, add the tackifier emulsion identical, obtain the binder composition of example 10 with example 1 with same ratio.Use said composition to make double-sided adhesive sheet by the method identical with example 1.
＜example 11 〉
Except using AA2 part and MAA3 part to replace operating equally with example 1 AA4 part, obtain acrylic polymer emulsions (below be also referred to as " emulsion E11 ").In this emulsion E11 with same ratio add with example 1 in the used identical tackifier emulsion of tackifier emulsion, obtain the binder composition of example 11.Use said composition to make double-sided adhesive sheet by the method identical with example 1.
＜example 12 〉
Except using AA3 part and MAA3 part to replace operating equally with example 1 AA4 part, obtain acrylic polymer emulsions (below be also referred to as " emulsion E12 ").In this emulsion E12 with same ratio add with example 1 in the used identical tackifier emulsion of tackifier emulsion, obtain the binder composition of example 12.Use said composition to make double-sided adhesive sheet by the method identical with example 1.
To constituting the acrylic polymers of above-mentioned each acrylic polymer emulsions E10～E12, similarly measure Mw and Gc with emulsion E6～E9.In addition,, similarly make emulsion with the corresponding indicator polymerization thing of the acrylic polymers that constitutes each emulsion, obtain the Ga of this indicator polymerization thing with example 1 for above-mentioned each emulsion E10～E12.At this moment, for emulsion E10, it is 4 hours with removing the dropping time set of emulsion that the silanol base forms the raw material monomer of the composition behind the property monomer.In addition, similarly measure the gel fraction (Gb) of each tackiness agent of example 10～example 12 with example 1.The measurement result of above-mentioned Mw, Gc and Gb is as shown in table 4.In addition, indicator polymerization thing Ga is about 14% in emulsion E10～E12.The vinylformic acid that contains in the raw material monomer that in this table 4, is simultaneously displayed on the kind of the acrylic polymer emulsions of using in the preparation of binder composition of example 10～example 12 and in the making of each emulsion, uses and the amount of methacrylic acid.
Table 4
Emulsion AA (part) MAA (part) Mw(×10 4) Gc(％) Gb(％)
Example 10 E10 1 3 65.8 44.0 33.5
Example 11 E11 2 3 69.7 39.6 34.4
Example 12 E12 3 3 68.3 41.4 39.8
With the double-sided adhesive sheet that makes in example 10～example 12 after the making in preserve under 50 ℃ the environment carried out slaking in 3 days after, use the adhesive sheet of this double-sided adhesive sheet and example 6～example 9 similarly to estimate stripping strength, high temperature coherency, end is peeled off and the anti-rebound resilience of foams.Its result is as shown in table 5.
Table 5
Stripping strength [N/20mm] Coherency [mm/hr] End is peeled off [mm] The anti-rebound resilience of foams [mm]
Example 10 12.1 2.0 0.1 0.8
Example 11 13.6 1.0 0.2 4.8
Example 12 13.0 1.1 0.1 3.1
As shown in table 5, and the adhesive sheet of the example 10～example 12 that obtains with AA and MAA all shows the stripping strength that about 12N/20mm is above, in the test of high temperature coherency, do not see that test film drops midway, peeling off in the stripping test highly is 2mm following (further following for 0.5mm) and peeling off highly below 5mm in the anti-resiliency test of foams endways.That is, peel off preventing property and these 4 characteristics of the anti-rebound resilience of foams with high-level equilibrium ground realization tackiness, high temperature coherency, end.
As shown in table 5, when the total amount of AA and MAA is more than 5 parts the time, the anti-rebound resilience of foams has the tendency of decline sometimes.Also confirm in addition: all operate equally with example 6 and adhesive sheets of obtaining except the amount of the AA that will contain in the raw material monomer changes to 2 parts all the other from 4 parts, to compare the high temperature coherency low with the adhesive sheet of example 6.These results show: the preferred especially raw material monomer that contains the 3 parts～about 4.5 parts ethene unsaturated monocarboxylic acid (preferred AA and MAA) of having an appointment with respect to 100 parts of totals of (methyl) alkyl acrylate that uses.
More than object lesson of the present invention is had been described in detail, but these are illustration, and non-limiting claim.The technology of putting down in writing in the claim comprises various distortion, the change of above illustrative object lesson.
As mentioned above, if adopt aqueous adhesive composition of the present invention, then can form and to realize tackiness, high temperature coherency and the terminal adhesive sheet of peeling off the binder layer of preventing property and having this binder layer with high-level equilibrium ground.For example, can form the adhesive sheet that has thicker (thickness of for example about 50 μ m～about 100 μ m) and all realize the binder layer of above-mentioned 3 characteristics with high level.Composition of the present invention is suitable for having the adhesive sheet of above-mentioned binder layer, the manufacturing of for example double-sided adhesive sheet (comprising double sticky tape).In addition, according to the present invention, provide with high-level equilibrium ground realize under tackiness, the hot environment coherency and to the adhesive sheet of the tracing ability (curved surface tackiness) of the surface shape that is attached body.Described adhesive sheet is brought into play above-mentioned characteristic, is suitable as the self adhesive tape that automobile interior trim material for example uses (automobile interior trim material is the double-sided adhesive sheet etc. of usefulness fixedly).

Claims (6)

1. aqueous adhesive composition is to be scattered in aqueous adhesive composition in the water based on acrylic polymers and this acrylic polymers, it is characterized in that, satisfies following each condition:
Described acrylic polymers be adopt azo-initiator, will be that the raw material monomer of principal monomer is polymerized with (methyl) alkyl acrylate;
The weight-average molecular weight of the solvable composition of tetrahydrofuran (THF) of described acrylic polymers is 65 * 10 4～100 * 10 4
Described raw material monomer contains silanol base formation property monomer;
Described raw material monomer is when removing composition after described silanol base forms the property monomer carry out polymerization from this raw material monomer, and the mass ratio that forms the insoluble composition of ethyl acetate is the raw material monomer of 7～17% polymkeric substance; And
The insoluble composition of ethyl acetate form by described binder composition crosslinked after tackiness agent in shared mass ratio be 20～55%.
2. composition according to claim 1; wherein; it is dialkoxy silicane or the trialkoxy silane with (methyl) acryl that described silanol base forms the property monomer, and this organoalkoxysilane had 2 or 3 alkoxyl groups is to be independently selected from methoxyl group and the oxyethyl group any respectively.
3. composition according to claim 1, wherein, copolymerization has described silanol base formation property monomer in described acrylic polymers, and the ratio that described silanol base formation property monomer accounts for the total amount of described raw material monomer is 0.005～0.035 quality %.
4. composition according to claim 1, wherein, described acrylic polymers is will contain described silanol base by the chain-transfer agent that to use with respect to these raw material monomer 100 mass parts be 0.025～0.035 mass parts to form the monomeric raw material monomer of property and carry out letex polymerization and obtain.
5. composition according to claim 1, wherein, also containing with respect to described acrylic polymers 100 mass parts is the tackifier of 5～40 mass parts.
6. an adhesive sheet has the binder layer that uses the described aqueous adhesive composition of claim 1 and form.
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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4766571B2 (en) 2007-11-22 2011-09-07 日東電工株式会社 Aqueous pressure sensitive adhesive composition and use thereof
CN102464960B (en) * 2010-10-29 2014-10-15 第一毛织株式会社 Adhesive composition, optical member, surface protective film, and adhesive sheet
TWI546358B (en) * 2012-12-11 2016-08-21 鴻海精密工業股份有限公司 Pressure sensitive adhesive and synthesis method of making a polymer used for the same
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1566245A (en) * 2003-06-09 2005-01-19 日东电工株式会社 Water dispersible adhesive composition, adhesive sheet and rubber foam adhesive sheet employing the same
CN1612921A (en) * 2002-10-04 2005-05-04 琳得科株式会社 Pressure sensitive adhesive film for overlamination

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0768499B2 (en) 1988-12-02 1995-07-26 株式会社日本触媒 Aqueous dispersion type pressure sensitive adhesive composition
JPH0726229A (en) * 1993-07-07 1995-01-27 Nippon Carbide Ind Co Inc Water-dispersed acrylic pressure-sensitive adhesive composition
KR960007660A (en) * 1994-08-12 1996-03-22 Acrylic sheet, acrylic adhesive sheet and manufacturing method thereof
DE69517436T2 (en) * 1994-08-12 2000-10-12 Avery Dennison Corp., Pasadena TAPE-MADE, PRESSURE-SENSITIVE EMULSION ADHESIVE
JP3123378B2 (en) 1994-12-15 2001-01-09 ジェイエスアール株式会社 Water-based pressure-sensitive adhesive
JP2000319610A (en) * 1999-05-14 2000-11-21 Nitto Denko Corp Adhesive tape for sealing corrugated fiberboard
JP4530484B2 (en) * 1999-08-25 2010-08-25 日東電工株式会社 Water-dispersed pressure-sensitive adhesive composition, method for producing the same, and pressure-sensitive adhesive sheet
JP2001316652A (en) * 2000-05-11 2001-11-16 Nitto Denko Corp Adhesive composition and adhesive tape or sheet
JP4386601B2 (en) 2001-09-05 2009-12-16 日本カーバイド工業株式会社 Acrylic pressure-sensitive adhesive aqueous composition
JP2004189933A (en) 2002-12-12 2004-07-08 Ipposha Oil Ind Co Ltd Aqueous emulsion type adhesive composition
US7008987B2 (en) * 2003-06-10 2006-03-07 Nitto Denko Corporation Aqueous dispersion type pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and pressure-sensitive adhesive rubber foam sheet using the sheet
US7045568B2 (en) * 2003-08-13 2006-05-16 Nitto Denko Corporation Aqueous dispersion type pressure-sensitive adhesive composition, and pressure-sensitive adhesive sheet
JP4707984B2 (en) * 2004-08-06 2011-06-22 日本合成化学工業株式会社 Re-peelable water-based adhesive composition
JP4839707B2 (en) * 2005-07-12 2011-12-21 Ｄｉｃ株式会社 Double-sided adhesive tape and method for producing double-sided adhesive tape
JP5220991B2 (en) * 2005-10-18 2013-06-26 日東電工株式会社 Water-dispersed pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet
JP5403865B2 (en) * 2006-03-01 2014-01-29 日東電工株式会社 Adhesive sheets
JP2007302753A (en) 2006-05-10 2007-11-22 Toho Earthtech Inc Amine-based curing agent composition
JP5095150B2 (en) * 2006-08-03 2012-12-12 日東電工株式会社 Aqueous pressure sensitive adhesive composition and use thereof
JP4458546B2 (en) * 2006-12-07 2010-04-28 日東電工株式会社 Method for producing double-sided adhesive pressure-sensitive adhesive sheet
JP4766571B2 (en) * 2007-11-22 2011-09-07 日東電工株式会社 Aqueous pressure sensitive adhesive composition and use thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1612921A (en) * 2002-10-04 2005-05-04 琳得科株式会社 Pressure sensitive adhesive film for overlamination
CN1566245A (en) * 2003-06-09 2005-01-19 日东电工株式会社 Water dispersible adhesive composition, adhesive sheet and rubber foam adhesive sheet employing the same

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EP2062954A1 (en) 2009-05-27
CN101440264A (en) 2009-05-27
EP2062954B1 (en) 2010-03-03
DE602008000751D1 (en) 2010-04-15
US20090137726A1 (en) 2009-05-28
JP4780676B2 (en) 2011-09-28

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